Method of chlorinating aliphatic chainsubstituted aromatic hydrocarbons



Patented Aug. 1, 1961 N Drawing. Filed Apr. 27, 1959, Ser. No. 808,94623 Claims. (Cl. 204-163) 7 organic compounds which are valuable aschemical intermediates in the synthesis of glycols and esters and alsohave been found useful in pesticidal applications such as in the controlof insect and nematode growth.

Prior methods in the chlorination of compounds of the above type,specifically for the chlorination of xylenes, have ordinarily beencarried out by dissolving the xylene in a solvent, such as carbontetrachloride, mixing or bubbling chlorine through the mixture while thechlorination is catalyzed either by light or an oxidizing agent. Thesechlorinated products are then isolated by distillation at reducedpressure or through separation by crystallization.

It is known that in order to avoid ring chlorination of xylenes,chlorination must be carried out in the absence of metallic ions,particularly iron, aluminum and zinc ions. If the reaction mixture isnot free of metallic ions,

i.e., having a concentration of no more than .0004% (4 ppm.) metal ions,a substantial amount of undesirable byproducts, such as ring-chlorinatedxylenes and polymerized byproducts, are formed reducing the commercialfeasibility and also the quality and purity of yield. This isparticularly true in higher chain-chlorinated xylenes, such ashexa'chloro-p-xylene and hexachloro-m-xylene; however, preparation ofother chlorinated xylenes involves the same difficulties, e.g.,a,a-dichloro-p-xylene, u-chloro-p-xylene,a,a,o',a'-tetrachloro-p-xylene.

Therefore, the addition of a metal ion sequestering agent has been foundto be necessary in most instances, i.e., an agent which suppresses thedecomposition activity of metallic impurities.

Ordinarily, elimination of contaminating metal ions, such as iron, zinc,aluminum, iron oxide, and ferric chloride, is typically attempted byemploying glass or ceramiclined equipment. However, this is oftenunsuccessful in that although due caution is exercised, bits of rust,dirt or other impurities may be blown, dropped or in other ways placedin the reaction system. The present invention overcomes this drawback.

Broadly, the present invention is directed to a process of preparingaliphatic chain-chlorinated aromatic hydrocarbons which compriseschlorinating an aliphatic chainsubstituted aromatic hydrocarbon in thepresence of an organic phosphate, preferably triphenyl phosphate,triethyl phosphate, or other aromatic hydrocarbon soluble aryl or alkylphosphates or an aliphatic polyhydroxy-substituted hydrocarbon, such aspolyethylene glycol, polypropylene glycol, pentaerythritol and mannitol,preferably sorbital and alternately in the presence of a combination ofthese compounds, preferably in the presence of triphenyl phosphate ortriethyl phosphate alone.

. Organic phosphate as employed in the specification and claims isintended to refer broadly to compounds of the structure:

wherein R R and R are selected from the group consisting of alkylradicals, e.g., those alkyl radicals having from 1 to 30 carbon atomssuch as methyl, ethyl, propyl, butyl, octyl, decyl, and eicosylradicals, aryl radicals, e.g., phenyl and naphthyl radicals, hydroxyarylradicals, e.g., 2-hydroxyphenyl, 2-4-dihydroxyphenyl, Z-hydroxynaphthyl,haloaryl radicals, e.g., 2-chlorophenyl, 2,4- dichlorophenyl,2-bromopheny1, and 2-chloronaphthyl radicals, hydroxyalkyl radicals,e.g., 2-hydroxyethyl, dihydroxypropyl, and trihydroxyoctyl radicals. Anaryl phosphate is intended to refer broadly to the structure set forthabove wherein at least one of the R groups is aryl. Further, an alkylphosphate is intended to refer broadly to the above structure wherein atleast one of the R groups is alkyl.

Illustrative of aliphatic chain-substituted aromatic hydrocarbons whichmay be chlorinated by the practice of this invention are: ortho-,metaand para-xylenes, toluene, diethylbenzene, triethylbenzene,diisopropylbenzene, mesitylene, cymene, durene and ethylbenzene.

The process is typically carried out in a reactor formed of steel, ironor any other conventional material of construction, typically aglass-lined reactor, equipped with agitation means, chlorine inletmeans, hydrocarbon inlet, e.g., xylene inlet, temperature control meansand product outlet. The chlorination may be carried out generally at atemperature in the range of about 10 to 200 C., e.g., preferably at atemperature in the range of about 40 to C. The reaction is normallycarried to completion, i.e., as determined by evolution of the desiredamount of hydrogen chloride. The product desired will dictate the amountof chlorine to be added in view of the fact that essentially thestoichiometric amount or a slight excess normally is added. Asubstantial excess of chlorine may be desirable in certain instanceswhere a highly chlorinated material is desired such as in thechlorination of xylene to produce06,05,a,0t,0t,ot'dlfiXilChlOl'O-P-XYlGHE. However, by employing lessthan the theoretical amount of chlorine required, over-chlorinatedproducts, such as a, x,u',a-tetrachloro-p-xylene anda,ot,u-trichloro-p-xylene in the preparation of a,a-dichloro-p-xyleneand a-chloro-p-xylene, will be substantially avoided.

The organic phosphate, either alone or with sorbitol, is generally addedto the aliphatic chain-substituted aromatic hydrocarbon before theinitial chlorination. Generally, .0Ol% to 1%, e.g., .0l% to 1% by weightof organic phosphate alone or together with .001% to 1%, e.g., 01% to 1%of sorbitol will substantially stabilize and prevent decomposition ofthe chlorinated product. Although it is desired that such a sequesteringagent or agents be added before the initial chlorination step, incertain instances, it may be desirable to add the sequesterant duringthe chlorination should the chlorination mixture become contaminatedwith metallic ions. Ordinarily, less than 1% by weight of triethylphosphate, triphenyl phosphate or sorbitol alone, or in combination,will satisfactorily depress the activity of metal ion contaminants;however, in certain instances, a higher concentration may be desirabledue to excessive contamination, e.g., a concentration as high as 5%sorbitol and organic phosphate, either singly or in combination.

An illustrative application of the sequestering agent of the presentinvention is that in which p-xylene is chlorinated in the preparation ofa,a,a,a',a',u'-hexachloro-pxylene. In this reaction, typically 2 to 4moles of pxylene are charged to a reactor in combination with 0.1% to1.0% based on the weight of xylene of sorbitol and organic phosphate,either alone or in combination. The reaction mixture is agitated andheated, i.e., to a temperature of about 50 to 70 C., and chlorine isadded at a rate which maintains good chlorine utilization efliciency.The chlorination is catalyzed by either illumination or a free radicalcatalyst, e.g., a mercury vapor lamp in a cooled immersion well as thesource of illumination. The source of illumination may also be any lightproducing actinic rays, e.g., fluorescent lamps, either white, blue orblack, or clear, unfrosted incandescent lamps. The reaction temperatureis gradually increased through the range of 50 to 150 C. duringchlorination. The chlorination is ended when the reaction product has aset point at a temperature between 95 to 100 C., i.e., when the chlorineutilization drops below about 1%.

Upon chlorination completion, excess chlorine and hydrogen chloride areremoved from the product by any convenient means such as blowing thereaction mixture with an inert gas, e.g., nitrogen or air while themixture is being held at a temperature of about 110 to 150 C. Thereaction product, i.e., the a,a,a,a',a,a-hexachloro-p-xylene is eitherfiltered and washed with an organic solvent, such as isopropanol, or thecrude chlorinated mixture is digested in isopropanol employing a volumeratio of isopropanol to a,a,a,a',a,a-hexachlorop-xylene of about 1 to 3.When employing isopropanol as the digesting solvent, the solventtemperature typically rises from about 30 to 40 C. to about 60 to 80 C.The resulting crystals are filtered and washed with isopropanol.Employing the triphenyl phosphate and sorbitol in combination with theisopropanol digestion, a product having a melting point between 106-112C. is obtained in pure yields of 70% to 90%.

A similar oz,0t,0c,a',oc',oc'heXaChlOTO-p-Xy1ene preparation viachlorination of p-xylene but employing no sequestering agent, i.e.,sorbitol and/or triphenyl phosphate, with an iron or metallic ioncontamination of .004% to .01% typically results in a decomposed highlypolymerized crude reaction mass which darkens before 0.25 mole ofchlorine per mole of xylene is added.

Another illustrative process within the scope of the present inventionis that comprising the use of triphenyl phosphate and sorbitol, eitherin combination or alone, in the preparation of lower alkylchain-substituted benzenes or naphthalenes having less than six chlorineatoms substituted on the lower alkyl groups, specifically 06,06dichloro-p-xylene (xylylene dichloride) and a-chloro-pxylene (xylylchloride). Typically, in this preparation, the reactants are combined inproportions of 1 mole of xylene to 0.9 to 1.8 moles of chlorine. Thechlorination is catalyzed by light or other means as above in thepreparation of a,oc,0c,at,oc',a'-h6XaChl0I0-p-Xylne; however, it iscarried out at a temperature between 30 and 70 C., e.g., 45 to 55 C., inthe absence of a solvent. From .001% to 1.0%, e.g., .01% to 1.0%, oftriphenyl phosphate and sorbitol, either alone or in combination, areadded to the xylene either before chlorination begins or whencontamination with metallic ions becomes apparent. The chlorinationtypically is carried out over a period of about 2 to 6 hours, and uponchlorination completion the crude mixture is cooled to about to 25 C.,precipitating the desired p-xylylene dichloride. The p-xylylenedichloride may be digested with a digesting solvent, e.g., isopropanol,typically at an elevated temperature, e.g., 60 to 80 C.

Alternately, the chlorinated reaction product may be isolated throughdistillation, the xylylene dichloride distilling at 115 to 128 C. at 5to 10 mm. mercury pressure. The sequestering agents of this inventionbeing high boiling solids do not contaminate the distilled lowerchlorinated reaction products; that is, the a-chloro-plowing specificexamples are offered.

EXAMPLE I Preparation of a,a'-dichlor0-p-xylene employing triphenylphosphate and sorbitol as sequestering and stabilizing agents Into athree-necked flask equipped with thermometer, addition tube andcondenser is placed 212 g. of xylene (2.0 mol) and 0.6 g. each ofsorbitol and triphenyl phosphate (0.3% by weight of xylene). 0.0012 g.of ferric oxide (4 p.p.m. iron) is added and the mixture is heated to atemperature of about 70 C. The triphenyl phosphate dissolves while thesorbitol remains and is only partially soluble. Chlorination is thencarried out by passing gaseous chlorine into the reaction mixture until1.6 mols of chlorine per mole of xylene is reacted, measured by theamount of hydrogen chloride evolution. During chlorination, the reactionis catalyzed by illumination from two blue 15-watt fluorescent lampsplaced about 2-3 inches away from opposite sides of the flask. Thesolution remains clear and colorless throughout the chlorination, thedesired product being isolated through distillation at reduced pressure.g. of a,a-dichloro-pxylene (34.0% pure yield) and a mixture of lowerchlorinated xylenes result, thus demonstrating that no decomposition orpolymerization results when employing these sequestering agents of thepresent invention.

EXAMPLE II Employing the procedure given in Example I,a,adichloro-p-xylene is prepared in the presence of iron, i.e., at aconcentration of 4 ppm. iron in the form of ferric chloride. Results ofthis preparation indicate that a,a'-dichloro-p-xylene may be prepared inbetter than 30% pure yield when the chlorination mixture is contaminatedwith ferric chloride if the sequestering agents of the presentinvention, i.e., triphenyl phosphate and sorbitol are employed.

EXAMPLE III Preparation of a,a'-dichlor0-p-xylene in the absence ofsequestering agents Employing the procedure given in Example I, 424 g.of p-xylene (4.0 mols) is added to 0.0024 g. of iron oxide (4 ppm.iron). No sorbitol or triphenyl phosphate is added to this mixture. Thereactants are heated to about 70 C. and gaseous chlorine is introduced;immediately a dark green color develops and before 0.25 mole of chlorineis added, the efficiency of the chlorination is reduced to the point atwhich chlorination stops, the reaction mixture being in such a statethat isolation of any product is uneconomical.

EXAMPLE IV Preparation of a,a'-dichloro-p-xylene in the presence of ironas ferric chloride and in the absence of sequestering agents Employingthe procedure given in Example III with the exception that thecontaminating ion is added in the form of ferric chloride is carriedout, a similar decomposed product is obtained, thus demonstrating thatin the presence of iron contamination, a sequestering agent isnecessary.

EXAMPLE v Preparation of a,a-dichloro-p-xylene in the presence ofcontaminating iron employing triphenyl phosphate alone as a sequesteringagent EXAMPLE VI Preparation of a,a,a,a',a,a-hexachloro-p-xyleneemploying triphenyl phosphate and sorbitol as sequestering andstabilizing agents 0.6 g. each of sorbitol and triphenyl phosphate (0.3%by Weight of xylene) are added to 212 g. of p-xylene (2.0 mols) in athree-necked flask, followed by the addition of 0.0012 g. of iron oxide(4 p.p.m. iron). The reaction mixture is heated to 70 C. and gaseouschlorine is introduced. The chlorination is catalyzed by illuminationfrom a clear 100-watt incandescent lamp placed about 2 inches from theflask. Following an induction period, the solution remains clear andcolorless. Upon addition of 0.7 mole of chlorine per mole of xylene, thereaction mixture is still clear and colorless. The chlorination iscontinued until 8.0 moles of gaseous chlorine per mole of xylene isadded, the temperature of the reaction mixture rising from 70 C. toabout 145 C. The reaction mixture is then combined with an equal volumeof chilled isopropanol, cooled and filtered, yielding a product having amelting point of 110-112 C. This demonstrates that although acontaminating amount of iron ion may be present, a significant yield ofthe desired hexachloro-p-xylene may be prepared when employing thesequestering agents of the present invention.

EXAMPLE VII Preparation of a,oz,a,a',a,a'-hexachloro-p-xylene in thepresence of contaminating metallic ions and in the absence ofsequestering and stabilizing agents The procedure given in Example VIpreviously is.

,carried out with the exception that the sequestering agents, i.e.,sorbitol and triphenyl phosphate, are omitted. Upon chlorination, acontaminated and highly decomposed product results.

EXAMPLE VIII Preparation of a-chloro-p-xylene in the presence oftriphenyl phosphate and sorbitol as sequestering agents and in thepresence of iron oxide as the contaminant EXAMPLE IX Preparation ofa,a,a,a,a,a,-hexachloro-p-xylene in the presence of triphenyl phosphateas a sequestering and stabilizing agent and in the presence of ironoxide as the contaminating agent employing the mother liquor from theinitial preparation of a,oz'-dichloro-p-xylene as a starting materialThe mother liquor from the initial preparation of a,ot'-dichloro-p-xylene given in Example I is mixed with 0.3% by weight of themother liquor of triphenyl phosphate (2.9 g.). 948 g. (6.0 mols) of themother liquor in combination with triphenyl phosphate is heated to about80 C. in a three-necked flask, whereupon gaseous chlorine is introduced,the temperature of the reaction mixture rises to about 140 C. Thereaction is catalyzed by actinic rays from two 15-watt fluorescent lampsplaced about 2-3 inches away from opposite sides of the flask. Uponevolution of 4.8 moles of hydrogen chloride per mole of the originalmother liquor, the reactant mixture is allowed to cool, resulting in1468 g. of the desired hexachloro-p-xylene (4.7 mols) which uponrecrystallization has a melting point of -109 C. This represents abetter than 60% yield based on the starting material, thus demonstratingthat in a continuous process, the sequestering agents of the presentinvention may be added at any stage of preparation to suppress thecontaminating action of metal ion in the reactant stream.

EXAMPLE X Preparation of a,a,a,a',a',a'-hexachloro-m-xylene in thepresence of iron oxide as a contaminating agent and in the presence oftriphenyl phosphate and sorbitol as sequestering agents The proceduregiven in Example VI in the preparation ofa,a,a,a',a',a'-hexachloro-p-xylene is repeated with the exception thatm-xylene is employed as the initial starting product. Upon chlorinationcompletion, a significant yield of the desired hexachloro-m-xylene isobtained, thus demonstrating that m-xylene may be chlorinated in thepresence of contaminating metal ions when the chlorination is carriedout in the presence of the sequestering agents of the present invention.

EXAMPLE XI Preparation of a,a,a,a',a,u'-hexachloro-m-xylene in thepresence of contaminating iron oxide and in the presence of triphenylphosphate as a sequestering agent The procedure given in Example X iscarried out with the exception that triphenyl phosphate alone is used inplace of the triphenyl phosphate-sorbitol combination as sequesteringagent. Upon chlorination completion and isolation of the desiredproduct, little or no decomposition or polymerization is observed, thusdemonstrating that triphenyl phosphate is singularly effective as asequestering agent.

EXAMPLE XII Preparation of a,a,a,a',a',a'-hexachloro-p-xylene in thpresence of contaminating iron oxide and in the presence of triethylphosphate as a sequestering agent Into a three-necked flask equippedwith thermometer, addition tube and condenser are placed 212 g. ofxylene (2.0 mols) and 1.06 g. of triethyl phosphate (05% by weight ofxylene). 0.0012 g. of ferric oxide (4 p.p.m. of iron) are added and themixture is heated to a temperature of about 70 C. Chlorination is thencarried out by passing gaseous chlorine into the reaction mixture untilabout 8.0 moles of gaseous chlorine per mole of xylene are added. Duringchlorination, the reaction is catalyzed by illumination from twovlS-Watt fluorescent lamps placed about 2-3 inches away from the flask.When the reaction is completed, the reaction mixture is combined withchilled isopropanol, cooled and filtered, yielding a product which,without further purification or recrystallization, has a melting pointof 9495 C. The reaction mixture shows no discoloration duringchlorination dem- Qt,a',2,5 tetrachloro p xylene, a,oz,ct,ot',ot',a',2,5octachloro-p-xylene, ot,oc',4,6 tetrachloro-m-xylene,oc,cc',4-'t1ichloro-m-xylene oc,0c,ot,ot',oc',ot',4heptachloro-m-xylene, a, a,2,3,5,G-heptachloro-p-xylene, u,a,ot',a',2,5hexachlorop-xylenes, may also be prepared by employing the organicphosphates alone or in combination with sorbitol according to theinstant teachings. It is known in the art that ring-chlorinated xylenesare prepared by chlorination in the presence of metallic ions, i.e.,iron oxide or ferric chloride, and it is also known that subsequentlythese ring-chlorinated compounds may be chain-chlorinated by removingthe metallic ion and chlorinating in the presence of actinic radiation.However, it has been found that it is extremely diflicult to remove themetallic ion producing decomposition of the desired chain-chlorinatedcompound. It has been found that this difficulty may be overcome by theemployment of the sequestering agents of the present invention; that is,upon completion of ring chlorination, the resulting chlorinated mixturemay contain as high as 4 ppm. contaminating metallic ion, addition of.001% to 5.0%, i.e., 01% to 2% of organic phosphate alone or incombination with 001% to 5.0%, i.e., .01% to 2%, sorbitol will sequesterthe decomposing of these metallic ions.

It is to be understood that although the invention has been describedwith specific reference to particular embodiments thereof, it is not tobe so limited, since changes and alterations therein may be made whichare within the full intended scope of this invention as defined by theappended claims.

What is claimed is:

1. The method of preparing a chain-chlorinated aliphaticchain-substituted aromatic hydrocarbon comprising chemically reactingunder the catalytic influence of actinic light gaseous chlorine and analiphatic chain-substituted aromatic hydrocarbon contaminated with metalions in the presence of an organic phosphate selected from the groupconsisting of aryl phosphates and alkyl phosphates.

2. The method according to claim 1 wherein the organic phosphate istriphenyl phosphate and comprises about 001% to 1.0% by weight of thealiphatic side chain-substituted aromatic hydrocarbon.

3. The method according to claim 1 wherein the organic phosphate istriethyl phosphate and comprises about 001% to 1.0% by weight of thealiphatic side chain-substituted aromatic hydrocarbon.

4. The method of preparing chain-chlorinated methyl benzenes whichcomprises combining in the presence of contaminating metal ions a methylbenzene and an organic phosphate selected from the group consisting ofaryl phosphates and alkyl phosphates, introducing gaseous chlorine andagitating the reaction mixture under the catalytic influence of actiniclight, and maintaining a temperature in the neighborhood of about C. to200 C.

5. The method according to claim 4 wherein the organic phosphate istriphenyl phosphate.

6. The method according to claim 4 wherein the organic phosphate istriethyl phosphate.

7. The method according to claim 4 wherein the organic phosphatecomprises about .001% to 1.0% by weight of the methyl benzene.

8. The method of preparing chain-chlorinated xylenes which comprisescombining in the presence of contaminating metal ions xylene and anorganic phosphate selected from the group consisting of aryl phosphatesand alkyl phosphates, introducing gaseous chlorine, agitating thereaction mixture under the catalytic influence of actinic light, andmaintaining a temperature in the neighborhood of about 10 C. to 200 0,wherein the organic phosphate comprises about 001% to 5.0% by weight ofthe xylene.

9. The method according to claim 8 wherein the organic. phosphate is.triphenyl phosphate.v

10. The method according to claim 8 wherein the organic phosphate istriethyl phosphate.

11. The method of preparing a,a'-dichloro-p-xylene which comprisescombining in the presence of contaminating metal ions xylene and anorganic phosphate selected from the group consisting of aryl phosphatesand alkyl phosphates, wherein the organic phosphate comprises about.001% to 5.0% by weight of the xylene, heating the mixture to about 10to C., introducing gaseous chlorine at a ratio of about 1 to 3 moles ofchlorine to each mole of xylene and agitating the reaction mixture underthe catalytic influence of actinic light.

12. The method according to claim 11 wherein the organic phosphate istriphenyl phosphate.

v13. The method according to claim 11 wherein the organic phosphate istriethyl phosphate.

14. The method of preparing Ot-ChIOI'O-P-XYIBIIC which comprisescombining in the presence of contaminating metal ions xylene and anorganic phosphate selected from the group consisting of aryl phosphatesand alkyl phosphates, wherein the organic phosphate comprises about 001%to 5.0% by weight of the xylene, heating the mixture to about 10 to 100C., introducing gaseous chlorine in a ratio of about 0.5 to 2 moles ofchlorine to each mole of xylene and agitating the reaction mixture underthe catalytic influence of actinic light.

15. The method according to claim 14 wherein the organic phosphate istriphenyl phosphate.

16. The method according to claim 14 wherein the organic phosphate istriethyl phosphate.

17. The method of preparing a,a, x,a',a',a-hexachlorop-xylene whichcomprises combining in the presence of contaminating metal ions xyleneand an organic phosphate selected from the group consisting of arylphosphates and alkyl phosphates, wherein the organic phosphate comprisesabout .001% to 5.0% by weight of the xylene, heating the mixture toabout 10 to 100 C., introducing gaseous chlorine in a ratio of about 6to 12 moles of chlorine to each mole of xylene, agitating the reactionmixture under the catalytic influence of actinic light, increasing thetemperature of the reaction mixture to a maximum of about 200 C. duringchlorination and separating the chlorinated product.

18. The method according to claim 17 wherein the organic phosphate istriphenyl phosphate.

19. The method according to claim 17 wherein the organic phosphate istriethyl phosphate.

20. The method of preparing 06,!1,0t,0L',0t',Ot'-h6XaChlOI'O- m-xylenewhich comprises combining in the presence of contaminating metal ionsxylene and an organic phosphate selected from the group consisting ofaryl phosphates and alkyl phosphates, wherein the organic phosphatecomprises about .001% to 5.0% by weight of the xylene, heating themixture to about 10 to 100 C., introducing gaseous chlorine in a ratioof about 6 to 12 moles of chlorine to each mole of xylene, agitating thereaction mixture under the catalytic influence of actinic light,increasing the temperature of the reaction mixture to a maximum of about200 C. during chlorination and separating the chlorinated product.

21. The method according to claim 20 wherein the organic phosphate istriphenyl phosphate.

22. The method according to claim 20 wherein the organic phosphate istriethyl phosphate.

23. The method of preparing xylene derivatives having chlorine atomssubstitute both on the ring and the side chain which compriseschemically reacting in the presence of contaminating metal ions gaseouschlorine and a xylene having chlorine substituted only on the ring,which reaction is carried out in the presence of an organic phosphateselected from the group consisting of triphenyl phosphate and triethylphosphate and under the catalytic influence of actinic light.

(References on following page) 10 References Cited in the file of thispatent FOREIGN PATENTS 6 259,329 Great Britain Oct. 14, 192 UNITEDSTATES PATENTS OTHER REFERENCES 2,446,430 Norton 3 1948 5 Ellis:Chemistry of Petroleum Derivatives, vol. I

2,817,633 Mayor Dec. 24, 1957 (1934), PP-

1. THE METHOD OF PREPARING A CHAIN-CHLORINATED ALIPHATICCHAIN-SUBSTITUTED AROMATIC HYDROCARBON COMPRISING CHEMICALLY REACTINGUNDER THE CATALYTIC INFLUENCE OF ACTINIC LIGHT GASEOUS CHLORINE AND ANALIPHATIC CHAIN-SUBSTITUTED AROMATIC HYDROCARBON CONTAMINATED WITH METALIONS IN THE PRESENCE OF AN ORGANIC PHOSPHATE SELECTED FROM THE GROUPCONSISTING OF ARYL PHOSPHATES AND ALKYL PHOSPHATES.